Acyl derivatives of azo dyestuffs and process of preparing same



Patented Apr. 30, 1940 ACYL DERIVATIVES OF AZO DYESTUFFS AND PROCESS'OF Pl-EEPARING: SAME Charles Graenacher, Riehen, Franz Ackermann, Binningen, and Heinrich Bruengger, Basel; Switzerland, assignors to Society of Chemical Industry in Basle, Basel, Switzerland No nrawiag; Application July'll, 1939, Serial N0. 283,872. In Switzerland August 1'7, 1935 13 Claims. (01. 260-203) The present invention relatesto a new process for converting into acyl derivatives water-insoluble azo dyestufis obtained from diam-compounds and arylides from aromatic hydroxy-carboxylic acids, which acyl derivatives are characterized by an increased solubility in water. This invention comprises the new process, as well as the newacyl derivatives of the insoluble azo dyestuffs from diazo-compounds and arylides from aromatic hydroxy-carboxylic acids.

It has been found that quitev generally the water-insoluble azo dyestuffs which are described in the literature in great number and are ob-' tained from diazo-compounds and arylides from aromatic hydroxy-carboxylic acids, can be converted into new acyl derivativeswhichare characterized by their'solubility in water, by causing these water-insoluble azo dyestuffs to react in the presence of tertiary bases with acylating agents which are derived from organic acids containing more than one salt-forming group, which group itself is selected from the group consisting of carboxyl groups and sulfonic groups.

The new products are therefore acyl derivatives of azo dyestuffs which are themselves free from carboxyl groups and sulfonic groups and are characterized by the atomic grouping wherein R1 stands for a member of the group consisting of aromatic nuclei. of the benzene and of the naphthalene series, R2 stands for the nuclear radical of an aromatic hydroxy-carboxylic acid and R3 stands for a member of the group consisting ofaromatic nuclei of the beno zene and of the naphthalene series, and wherein the azo-group and the-OI-I-group stand in orthoposition to each other, in which azodyestufis the two hydrogen atoms are replaced by the acyl radical of an organic acid which contains more than one salt-forming group from the group consisting of carboxyl and sulfonic' groups, which acyl derivatives form alkali salts which are soluble in water with formation of solutions from which the insoluble parent azo dyestufi can be precipitated by treatment with alkalies. These new products are characterized by the'solubility of their salts in water, and by the property of regenerating the insoluble parent dyestuffs merely by the action of saponifying agents.

The azo dyestuffs serving as parent materials .to' one another by bridges, phenyl linkage, the a,

in the present invention may belong to the series of the mono-, disor polyazodyestuffs. They may be obtained from the diam-compounds or various amines of the benzene and of the naphthalene series, and it-is explicitly pointed out that this expression includes also polynuclear diazotizing bases in which the aromatic nuclei are united for example the dithe triazine nucleus or --N=-Nlinkages. Therefore, such diazotizing bases are also'benzidine, dianisidine, 4 :4 -diaminodiphenylurea, monobenacyl-para-phenylene-diamine, aminoaz'obenzene, aminobenzene-azo-naphthalene and the likei' As coupling components' arylides of aromatic hydroxy carboxylic acids-may be used forexam- I ple such components which are derived from aromatic hydroxy-carboxylic acids of the benzene series, for instance the arylids of the phenol-', creSl-, xylenol and chlorocresol-carboxylic acids, and which are constituted in such a manner that they react with diazo compounds to form orthohydroxyazo dyestufis. Particularly suitable arylides are derived from polynucleararomatic hy-- droxy-carboxylic acids. Such arylides are for example the arylides of the 2z3-hydroxynaphthoic acids, of the lz4-hydroxynaphthalene carboxylic acid or of the 2:3-hydroxyanthracen'e carboxylic acid; further the arylides of the hydroxycarbaz'ole-carboxylicacids or of thenaphthocarbazole-carboxylic acids which are to be regarded as.

aromatic hydroxy-carboxylic acids, since the OH- group and the COOI-I-group are linked to aromatic nuclei. j I

Reference is made moreover to the numerous publications in the literature relating to such.

than one salt-forming igroup selected-itself from,

the group consisting of carboxyl groups and sulfonic groups, there may be mentioned halides of polycarboxylic acids, such as for example benzene-l23:5-tricarboxylic acid, benzene hexacarboxylic acid, and polysulfonic acids, such as for example 1:3-benzene-disulionic acid, 1:3:6- naphthalenetrisulfonic acid: further there are quite particularly suitable halides of sulfo-carboxylic acids inwhich both the sulfonic group and the carboxyl group are in the form of their halides, and those in which only the sulfonic groups or only the carboxyl groups are in the form of their halides. Examples of such compounds are the halides of the sulfobenzoic acids, of the sulfo-naphthoic acids, of thesulfo-acetic acid, and the like.

The acylation itself is carried out in the presence of a tertiary base which is also preferably used as reaction medium. Among the tertiary bases those are particularly suitable which are 'heterocyclic tertiary nitrogen bases for instance pyridine, piooline, quinoline, :acridine, thiazol, 2:4-dimethylthiazol or benzothiazol, of which the nitrogen atom is a member of the heterocyclic ring :to which it is linked by a simple bond, on

the one hand, and by a'double bond, on the other. For carrying out the reaction the halides of the above-mentioned acids or the analogues thereof need not be isolated. On the contrary, the reaction product of a phosphorous halide, such asi for example aphosphorous trichloride -or pentachloride, on the corresponding acidsmay be used directly. One may also proceed in such a manner that a solution of the am dyestufi and the polyvalent acid is treated in the tertiary base with phosphorous pentachl'oride or phosphorous trichlor'ide.

The derivatives obtainable by the invention give valuable transformation products, and can be used for dyeing the most varied materials, for example vegetable fibers, animal fibers, such as wool, silk, leather, or artificial fibers, such. as regenerated cellulose or cellulose derivatives, and artificial masses.

They are more or less readily soluble in water. Their aqueous solutions or suspensions may be used for dyeing and printing any desired material in such a manner that the goods, after having been dyed, gpadded or printed by known processes, are subjected to a saponifying treatment for example with alkalis or agents developing basic substances, such as ammonia, sodium carbonate, caustic soda solution, trisodium phosphate or alkali acetate, whereby the dye initially acylated is fixed as a pigment on the material, and particular is rendered fast to washing. The saponification of the acylated dyestufis can I also be effected in lacquers and artificial masses.

In many cases the treatment with saponifying agents can be applied in the dyeing operation.

If dyes are used which can form metallic .com-

,plexes, a treatment with a compound yielding a metal can be applied before, during or after the .saponification on the fiber, in the dye bath, in lacquers and artificial masses or to the dye in substance, whereby a metalliferous pigment is deposited on the fiber or in the material, or the dye in substance is converted into a metalliferous pigment.

In contradistinction to the soluble acyl dcrivatives of the leuco-compounds of vat dyes, the derivativesproduced by this invention need no oxidizing agent for their development.

The following examples illustrate'the invention, the parts being by weight:

'b-le in water.

Example 1 12.6 parts of the azo dye (melting point 262- 263 C.) produced by coupling diazotized l-arninonaphthalene and 2:3-hydroxynaphthoic acid anilide are dissolved by boiling in the necessary quantity of pyridine. The solution is cooled to C. and 19.2 parts of the dichloride of metasulfobenzoic acid are poured in. A brown solution isformed. A test portion of the solution, removed evenafter a short time, does not revert to the parent dye when poured into water, but after stirring gives a perfectly clear solution. After stirring for an hour, the main part of the pyridine is distilled in a vacuum and the residue of the distillation is triturated with a little hot water to remove the more easily soluble products. The washingfiuid, after cooling, contains very little of the acylated derivative, and is thrown away, and the radical is again Washed with a little water and then dried in a vacuum at C. A solid dark product is obtained which dis solves in water to a brown-red solution. A hot solution of the acylated derivative reverts completely after adding alkali, to the parent dye, which, after recrystallizing from toluol has the original melting point of 262263 C.

Example 2 19.2 parts of 3:5-benzoic acid disulfochloride are added to 100-120 parts of pyridine and 9.2

parts of the axo dye produced by coupling diazotized 4-chloro-ortho-toluidine and 2:3-hydroxynaphthoic acid-2-methyl-4-methoxyanilide are added. After heating quickly to 70-90" C. with thorough stirring the reaction is complete in about '10 minutes and the'product is readily solu- The main part of thepyridine is nov. distilled in a vacuum and the residue of the distillation is dissolved in a little water. By pouring the solution, if desired neutralized with sodium phosphate, into cold saturated brine the product is precipitated after some time, and the pure solid product can "be obtained from the solid saline product by extraction with alcohol. It is readily soluble in cold water and reverts to the parent dye on; addition of alkali.

Example 3 cohol the ester ofthe hydroxyazo dye is obtainedin. pure form. It is readily soluble in water to a red-brown solution, and reverts to the parent dye on saponification with dilute alkali.

. Example 4 8.8 parts of benzoic acid-3-sulfochloride and 4.2 parts of the azo dyestuff from diazotize'd l-aminonaphthalene and 2:3-hydroxynaphthoic acid'anilid'e are heated together to about -120 C. for 1-2 hours in 26 parts of quinoline, While stirring. After this time the bluish red color of the reaction mixture has changed into a yellow brown which is due to the acylation which has taken place. The mixture is then poured into dilute hydrochloric acid whereby the sparingly.

The pyri dissolves in dilute ammonia to a brown solution.

brown solution. This solution becomes imme- On heating this solution the insoluble parent azo dyestufl which has been reformed by saponification is again precipitated.

The following table gives the particulars of further products which can be produced by this invention:

- Color of aque- Azo dyestufl Acylatmg agent ous solution 1 l-naphthylamine 2:3-hydroxynaphthoic acid-anilide Benzoic acid-B-sullochlorlde Red-brown. 2 2:5-dichloram'hnc 2:3-hydroxynaphtboic acid-anilide do Orange-red. 3 do Benzoic acid-3:5-dis1fliochl0l'ide Do. 4 Amritnlochlqrag nslol (OCH3NH2C1:1,2,4) 2:3-hydr0xynaphthoic a 1- Benzoic acid-3-sulfochloride Red.

0 o-anisi 1 e. 5 Nitrotoluidine (OHaNHzN02:l,2,4)- 2:3-hydroxynaphthoicacid-anilide, do Orange. 6 Amritiliuochlqraiigol (0 CHaNH2C1I1,2.4) 2:3-hydroxynaphthoic ecid- Benzoic 3.8ld-325- di5l11f00h10fld8 Red.

0 o-amsi 1 e. 7 4-(4'-methyl)-phenoxyacety1arnino-2:5-diethoxy-1-amiuobenzcne 213- Benzoic acid-3-sulfochloride Brown. hydroxynaphthoic acid-anillde. 8 do Benzoic acid-3:5-disu1fochloride Do. 9 4-benzoylarnino-2:5-diethoxy-l-aminobenzene 2:3-hydroxy-naphtboic d acid-anillde. 4-chloro-2-aminodxphenylether i-carboxylic acid-diethylamide 2:3- Red.

hydroxynaphthoic acid-ortho-anisidido. l1 l-methoxy-2-aminobenzene4-diethyl-sulfamide 2:3-hydroxynaphthoic acid-2:4-dimethoxy-S-chloranisidide. l2 Chlortoluidine (OHaNHgClZLZA) 2-hydroxycarbazole-3-carboxylic Brown.

acid-para-chloranilide. l3 2:5-dichloraniline 2:3-hydtoxynaphthoic acid-ortho-anisidide Orange- 14 .do Orange-red. l6 4:4'-diaminodiphenylcarbamidee2:3-hydroxynaphthoic acid-anilide Brown-red. l6 4-chlorbenzene-azo-4-amino-3-methoxynaphthalene 2:3-hydroxy-naphd0 Brown-black.

thoic acid-anilide. 17 Z-mejhsd-i5g-diamino-5-methoxy-azobenzene 2z3-hydroxynaphthoic Benzoic acid-3:5-d1sulfochlor1de Red-brown.

aci -am 1 e. 18 4:4-diaminodipl1eny1methane 2:3-hydroxynaphthoic acid-anilide Benzoic ac1d-3-su1foch1or1de Orange-red. 19 4:4-diaminodiphenylether 2:3-hydroxynaphthoic acid-anilide do Red. 20 l-aminonaphthalene-e anilide of 2:3-hydroxynaphthoic acid. 1:3:6-naphthalene-trisulfochlot Brown. 21 Meta-chloraniline anilide of 2:3-hydroxynaphthoic acid. Benzene-1:3:5-tr1carboxyhc acid ch Orange. 22 Benzenehexacarboxylic acid-chloride. Do. 23 Naphthoic acid-disulfochlqride Do. 24 hydroxynaphthoic a id 1:3z6-naphthalene-trisulfon1c acid-chlori e Do. 25 4-(4-methyl)-phenoxyacetylamino-2:5-dimethoxy-1-a Furane-md-sulionecarboxyllc acid chlo- Brown.

ide of 2:3-hydroxynaphtho1c acid. ride. 26 2:5-dich]oraniline amaphtho-carbazolc-5-hydroxy-ortho-carboxylic a id- Beuzoic acid 215-.d1sulfo0hlor1de Do.

ortho-toluidide. 27 Nitrotoluidine (CH3.NH2.NO2:1,2,4) a-naphthocarbazo1e-3hydoxy-or- .d0 Du.

tho-carboxylic acid-anilide. 28 Nitroanisidine (OOH3.NHz.NOzZ1.2.4)-) Z-hydroxycarbazole-3-carboxyl- B nzolc ac1d-3-Sulf0chlor1de Do.

ic acid-ottho-toluidide. 29 Nitroanisidine (N Hz.0CH3.NOz21.2.4) 2-hydtoxycarbazole-3-carboxy]- .do Do.

ic acid-para-chloroanilide. 30 4-chloro-2-amino-l:Y-diphenylether 4-hydroxydiphenyl-s-carboxylic do Do.

acid-para-chloranilide. 31 Aminonitro-chlorobenzene (N H2.N02C1Z1.2.4) 3-hydroxydiphenylene- .do D0.

oxide-Z-carboxylic acid-4'-chloro-2-methoxyanilide. 32 Nitro'toluidine (N'Hz.NOg.CHa:l.2.4) 3-hydroxydiphenylsulfide-2- do Do.

carboxylic acid-4-chloro-2-methoxyanilide. I 33 4:4-damino-3:3dimethoxydiphenyl anilide of 2:3-hydroxynaphthoic .r... d0 Do.

aci V 1 34 kamifinoazo-benzene a-naphthylamide of the 2:3-hydroxynaphthoic ..d0 Do.

aci 35 4-amino-2-methoxybenzene-azo-naphthalene fl-naphthylamlde of the do Do.

2:3-hydroxynaphthoic acid. 36 Ohlorotoluidine (NH .CH3.Cl:l.2.5) fl-naphthylamide of the 2:3-hydo Brown-red.

droxynaphthoic acid. 37 Cgiorotoludine (NH:.CH3-C1I1.2.4) anilide of the 1:4-hydroxynaph- ...do Red. 010 am p 38 Para-nitraniline anilide of the 1:4-hydroxynaphthoic acid .-d0 Do. 39 2:5-dichloroaniline 2:3-hydroxynaphthoic acid-3'-benzoylaminoanilide 40 2:5-dichloroaniline arylide from 2r3-hydroxynaphthoic acid and 5aminobenzimidazolc. 41 2:5dieh1oraniline ary1ide from 2:3-hydroxynaphthoic acid and 1- Do.

amino-4:5-phenylaz1midobenzene. 42 4-benzoylamino-2z5-diethoxy-l-aminobenzenc 2:3-hydroxyanthracene do Brown.

carhoxylic acid anilide.

diately turbid on heating due to the decomposition to the insoluble parent azo dyestuff.

Example 5 8.8 parts of benzoic acid-3-sulfochloride and 4.2 parts of the azo dyestuff from diazotized 1 aminonaphthalene and 2t3-hydroxynaphthoic acid anilide are heated together to about 110-120 C. for 1-2 hours in 27 parts of benzothiazol, while stirring. The blue-red color of the reaction mixture changes thereby to a yellow brown due to acylation.

The reaction mixture is then poured into dilute hydrochloric acid whereby the acylation product is precipitated in resinous form as benzothiazol.

salt which is sparingly soluble in water. The aqueous solution is decanted and the residue dried in a vacuum.

The reaction product is a brown powder which This application is a continuation-in-part of our application Serial No. 92,244, filed July 23,

What we claim is:

1. Process for the manufacture of acyl derivatives of am dyestuffs comprising causing azo dyestuffs-which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from aromatic hydroxycarboxylic acid, to react in a medium consisting of a heterocyclic tertiary nitrogen base whose nitrogen atom is a member of the heterocyclic ring to which it is linked by a simple bond. on the one hand, and by a double bond, on the other. with halides of organic acids which con tain more than one salt-forming group from the group consisting of carboxyl groups and sulfonic groups.

2. Process for the manufacture of acyl derivatives of azo dyestufis oomprising'causing azo dyestuffs which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from aromatic hydroxy-carboxylic acid, to react in a medium consisting of pyridine, with halides of organic acids which contain more than one salt-forming group from the group consisting of carboxyl groups and-sulfonic groups.

3. Process for the manufacture of acyl derivatives of azo dyestuff, comprising causing azo dyestufis which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from polynuclear aromatic hydroXy-carboxylic acid, to react in a medium consisting of a heterocyclic tertiary nitrogen base whose nitrogen atom is a member of the heterocyclic ring to which it is linked by a simple bond, on the one hand, and. by a double bond, on the other, with halides of organic acids which contain more than one saltforming group from the group consisting of carboxyl groups and sulfonic groups.

4. Process for the manufacture of acyl derivatives of azo dyestuifs, comprising causing azo dyestuffs which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from polynuclear aromatic hydroxy-carboxylic acid, to react in a medium consisting of pyridine, with halides of organic acids which contain more than one saltforming group from the group consisting of carboxyl groups and sulfonic groups.

5. Process for the manufacture of acyl derivatives of azo dyestuffs, comprising causing azo dyestuffs which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from the 2:3-hydroxynaphthoic acid, to react in a medium consisting of a heterocyclic tertiary nitrogen base whose nitrogen atom is a member of the heterocyclic ring towhich it is linked by a simple bond, on the one hand, and by a double bind, on the other, with halides of a sulfocarboxylic acid.

6. Process for the manufacture of acyl derivatives of azo dyestuffs, comprising causing azo dyestuffs which are free from carboxyl groups and sulfonic groups and are obtained from diazo compounds and arylides from the 2:3-hydroxynaphthoic acid, to react in a medium consisting of pyridine, with halides of the benzoic-3-sul fonic acid.

'7. The acyl derivatives of the azo dyestuffs which are free from carboxyl groups and sulfonic groups and are characterized by the atomic roupin wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, R2 stands for the nuclear radical of an aromatic hydroxy-carboxylic acid and R3 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and wherein the azo-group and the OH-group stand in ortho-position to each other, in which azo-dyestuffs the two hydrogen atoms are replaced by the acyl-radical of an organic acid which contains more than one salt-forming group from the group consisting of carboxyl and sulfonic groups, which acyl derivatives form alkali salts which are-soluble in water with formation of solutions from which the insoluble parent azo dyestuff can be precipitated by treatment with alkalies.

8. The acyl derivatives of the azo dyestufis which are free from carboxyl groups and sulfonic groups and are characterized by the atomic grouping R -N=NRz C-N-Rs II I o H wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, R2 stands for the nuclear radical of a polynuclear aromatic hydroxycarboxylic acid, the azo-group and the CNR3 ll l

group standing in ortho-position to the OH- group, and R3 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and in which azo dyestufis the two hydrogen atoms are replaced by the acyl radical of an organic acid which contains more than one salt-forming group from the group consisting of carboxyl and sulfonic groups, which acyl derivatives form alkali salts which are soluhis in water with formation of solutions from which the insoluble parent azo dyestufi can be precipitated by treatment with alkalies.

9. The acyl derivatives of the azo dyestuffs which are free from carboxyl groups and sulfonic groups and are characterized by the atomic grouping wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and R3 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and in which azo dyestuffs the two hydrogen atoms are replaced by the acyl radical of an organic acid which contains more than one saltforming group from the group consisting of carboXyl and sulfonic groups, which acyl derivatives form alkali salts which are soluble in water with formation of solutions from which the insoluble parent azo dyestuff can be precipitated by treat ment with alkalies.

10. The acyl derivatives of the azo dyestuffs which are free from carboxyl groups and sulfonic groups and are characterized by the atomic grouping r f- O H wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and R3 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and in which azo dyestufis the two hydrogen atoms are replaced by the acyl radical of a sulfocarboxylic acid which is united with the radical of the azo dyestuff by its C=O-group, which acyl derivatives form alkali salts which are soluble in water with formation of solutions from which the insoluble parent azo dyestufi can be precipitated by treatment with alkalies.

11. The acyl derivatives of the azo dyestuffs which are free from carboxyl groups and sulfonic groups and are characterized by the atomic grouping wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series, and R3 stands for a member of the group consisting of aromatic nuclei of the benzene and 0f the naphthalene series, and in which azo dyestuffs the two hydrogen atoms are replaced by the acyl radical of a benzene sulfocarboxylic acid which is united with the radical of the azo-dyestufi by its 0:0- group, which acyl drivatives form alkali salts which are soluble in water with formation of fonic groups and are characterized by the atomic grouping R1'N=1TT GNRa t 1'1 wherein R1 stands for a member of the group consisting of aromatic nuclei of the benzene and of the naphthalene series and R3 stands for a member of the group consisting of aromatic nucleicf the benzene and of the naphthalene series, and in which azo dyestuffs the two hydrogen atoms are replaced by the acyl radical of a benzoic-B-sulfonic acid which is united with the radical of the azo dyestuff by its C=O-group, which acyl derivatives form alkali salts which are soluble in water with formation of solutions from which the insoluble parent azo dyestuff can be precipitated by treatment with alkalies.

CHARLES GRAENACHER. FRANZ ACKERMANN. HEINRICH BRUENGGER. 

